Chemical and metallurgical aspects of arsenical bronze: the case of arsenic-loss in prehistoric metal production

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A recent publication in the American Journal of Physical Anthropology describes how humans adapted to arsenic in Andean populations of the Atacama Desert. It is here, where the highest arsenic levels in the Americas are found (>1,000 µg/L). The local population though, the Camarones people, who live in this environment during the last 7,ooo years, have not presented any epidemiological emergencies.

So the authors of the study – Mario Apata, Bernado Arriaza, Elena Llop and Mauricio Moraga fom the Universidad de Chile in Santiago and the Universidad de Tarapacá – compared the frequencies of four protective genetic variants of the AS3MT gene associated with efficient arsenic metabolization, between the living populations of Camarones and two other populations historically exposed to lower levels of arsenic. They found higher frequencies of the protective variants in those people from Camarones than in the other two populations.

The higher frequency of protective variants in both northern Chilean populations indicates a long exposure to naturally arsenic-contaminated water sources. The data suggest that a high arsenic metabolization capacity has been selected as an adaptive mechanism in these populations in order to survive in an arsenic-laden environment.

However, one has to note that a third of the population does not have any of the protective genetic variants of the AS3MT gene and still does not show any significant signs of arsenicosis – further research is planned (or maybe they should visit Styria?).

Slightly over a century ago, poison was a common part of everyday life. Arsenic, the notorious metalloid, was used in all sorts of products, primarily in the inks and aniline dyes of beautifully printed wallpapers and clothing. Odorless and colorless, it went into food as food coloring, and it was used in beauty products, such as arsenic complexion wafers that promised women pure white skin, until as late as the 1920s. It was found in the fabric of baby carriages, plant fertilizers, medicines. It even was taken as a libido pill in Austria.

The literature of the era hints at the effects from arsenic poisoning. The main character in Charlotte Perkins Gilman’s 1892 short story “The Yellow Wallpaper,” for instance, descends into madness and believes that the source of her illness stems from the wallpaper in her room. “It makes me think of all the yellow things I ever saw—not beautiful ones like buttercups, but old foul, bad yellow things,” she says. “But there is something else about that paper—the smell!”There are numerous studies on William Morris’s arsenic-laden wallpapers, in particular, which were extremely popular during the late 19th century. Morris himself, a designer and artist, was also the heir to the world’s largest copper mine at the time, which produced arsenic dust due to mining activity. Not only did the mine cause massive environmental damage to the land around it, but many miners died of lung disease, according to a 2003 article in Nature. Morris’s famous phrase about the doctors who treated these miners was that they “were bitten by witch fever,” insinuating that the doctors were quacks when they diagnosed arsenic poisonings. He was unwilling to believe the catastrophe his businesses had caused.
As long as people get what they want, most people don’t think twice about it.

Using Morris’s phrase as a fitting title, the art historian and Victorianist Lucinda Hawksley’s new book, Bitten by Witch Fever, tells the story of the extensive use of arsenic in the 19th century. It includes pictures of objects and artworks made from substances that incorporated arsenic, and advertisements for arsenic-filled products for Victorian women, such as soap with a doctor’s certificate to ensure its harmlessness.I spoke to Hawksley about arsenic’s prevalence in 19th-century home decoration, clothing, food, and topsoil. Our conversation has been condensed and edited for clarity.

Haniya Rae: Why was arsenic so commonly used?Lucinda Hawksley: In mid-Victorian times, Pre-Raphaelite and Aesthetic artists were particularly sold on this vivid shade of green, found by the Swedish chemist Carl Wilhelm Scheele in the 18th century. The green color came from copper arsenite, known as Scheele’s Green, which is a form of arsenic and a byproduct of the copper industry.If you think about the brilliance of copper and the way that a patina begins to color metal, it’s a beautiful color. Chemists hadn’t thought about how poisonous arsenic was, which today would seem crazy to us—it was present in so many things. Victorians didn’t think it was a problem unless you ate it. They hadn’t made the connection that the same thing that created this amazing green, and that was immensely fashionable in the 1860s and 1870s, could be a problem. It wasn’t just the Victorians, though—Germany, the United States, Scandinavia, among others, were all using arsenic in common goods.

Rae: By the late Victorian period, though, people had started to figure out it was dangerous?Hawksley: Around the 1860s, the cases of arsenic poisoning started getting to the newspapers. One wallpaper manufacturer debuted arsenic-free wallpaper, but no one paid much attention to that, until more and more cases started appearing. By the 1870s, William Morris started to produce arsenic-free wallpapers. At this point, William Morris himself didn’t actually believe that the arsenic was the problem—he was simply bowing to public pressure. He thought because no one was ill in his house from the arsenic wallpaper, it must be something else that was causing the sickness.

Rae: What were a few of these cases?Hawksley: Factory workers were getting sick—and many died—because they were working with green arsenic dye. It was fashionable to wear these artificial green wreaths of plants and flowers in your hair that were dyed with arsenic. In wallpaper factories, workers were becoming really unwell, especially when they were working with flock papers, or papers with small fiber particles that stick to the surface. The workers would dye these tiny, tiny pieces of wool or cotton in green, and while doing so would inhale them and the particles would stick to their lungs. The manufacturing process created a lot of dust from the dye—the dust had arsenic in it—and this created major problems for the factory workers as the dust would stick to their eyes and skin. If there were abrasions on their skin, the arsenic could get directly into their blood stream and poison them that way as well.

When the newspapers started to point out that this was happening, most people didn’t care. It’s a bit like today. People will still buy a brand of chocolate even if there’s been a story on how the chocolate has been produced by slave labor. They buy coffee that was also produced by slaves. They buy clothes, even though it was made by bonded labor. As long as people get what they want, most people don’t think twice about it. If they were confronted with things face on, of course they wouldn’t buy these products.

Rae: Did Britain ever pass legislation about arsenic?

Hawksley: In 1903 century, the U.K. actually did pass legislation about the safe levels of arsenic levels in food and drink—even though often there are no safe levels at all—but Britain never passed laws around wallpaper or paint. By the time the regulations were passed on arsenic in food and drink, arsenic wallpaper and paint had fallen out of fashion, so it’s possible they didn’t see a reason to actually pass legislation against it. To this day, there still isn’t a law banning someone from making arsenic wallpaper or dye in Britain.Rae: But it was pretty bad before that point?Hawksley: Before legislation was passed, bakers used arsenic green as a popular food coloring. Sometimes, a baker was given flour or sugar with arsenic in it unknowingly, but other times it was used as a bulking agent. You wouldn’t believe the kinds of things that were put into Victorian foods as bulking agents. It wasn’t just arsenic, there were lots of weird things. Flour was expensive, so they would resort to adding other things.There was an orphanage in Boston and all these small children were getting really, really sick and they didn’t know why. It turned out that the nurses were wearing blue uniforms dyed with arsenic and they were cradling the children, who in turn were inhaling the dye particles.That’s another thing, too: Green was a color that was always seen as the culprit, simply because it was so desirable at the time, but many other colors used arsenic as well. When the National Archives did testing on the William Morris wallpapers, all of the colors used arsenic to some extent. These colors were exceptionally beautiful, and up until this point, it was not something they could achieve without the use of arsenic.Rae: Are there still remnants of arsenic mining today?Hawksley: It’s funny because as I was doing my research, I was having a conversation with an older woman about my work. She had memories of growing up in the 1930s near a town that had had a working copper mine nearby. Her mother had told her not to grow any vegetables, because at that time they had realized the dangers of arsenic dust and knew it was in the soil. But for a long time, people living near copper mines had no idea that arsenic dust was falling on the soil, and so their crops would absorb all this arsenic dust. Lots of people were getting sick, but no one seemed to understand why. I’m sure that must have been the case with mining like this all over the world.

The last weeks I was busy with preparing roughly 300 samples for the data base and the hardness measurements. Samples were made of eight different alloys, four different annealing times at 600°C in reduced atmosphere, cross-section and longitudinal section, and up to five different grades of deformation (cold rolling). And I have to admit that the rolling machine is just fantastic! The more arsenic the alloy contains, the harder it was to roll (not very surprising…) but I was fascinated by the squeaky sound the higher alloyed metal produced.

I still remember wondering about the usage of arsenic in a prescription for hurting fingernails, which I read when I was eleven. The book was printed in 1731, and I loved to read through all the oddities it contained. The prescription explaines how to remove a fingernail without pain, and make it grow again:

Take gummi serapinum [Sagapenum], arsenic, both of the same quantity, powdered, and then make it with nut oil to a cream, put it on a fine cloth, and place all on the fingernail. The fingernail then can be removed without pain, then take a cold lye, and wash your toes or fingers with it.

The consumation of a pudding with arsenic was already noted earlier, as was the consumation of arsenic with bread or speck, e.g. for its performance-enhancing characteristics.

One of the earlier medicines against syphilis was made of arsenic and showed far less negative side effects than the previously used mercury (with severe side effects such as neuropathies, kidney failure, and severe mouth ulcers and loss of teeth). Arsphenamine (or Salvarsan / compound 606) was first synthesised in 1907 by P. Ehrlich and S. Hata and widely used (see also the “magic bullet“). The administration of treatment was complex requiring many injections over a long period of time, and it also produced toxic side effects, which were reduced by combining it with small doses of bismuth and mercury.

Salvarsan kit sold by W. Martindale

In the beginning of the 1940s, the arsenical compounds were supplanted as treatments for syphilis by penicillin. Not so in Eastern Germany; after the 2WW, the number of syphilis-infections rose dramatically, and Salvarsan or Neo-Salvarsan were not available. E. Schmitz (Magdeburg) managed to synthesise Neo-Salvarsan, which was sold as Arsaminol and later Neo-Arsoluin, and still contained arsenic; consequently, also syphilis infections dropped significantly in Eastern Germany.

Thanks to Benjamin Sabatini, who made me aware of this very kind complain about bad quality copper, and misbehaving merchants in Ur. The complaint is from around 1750 BC. I would like to know about something similar mentioning arsenic too!

When you came, you said to me as follows: “I will give Gimil-Sin (when he comes) fine quality copper ingots.” You left then but you did not do what you promised me. You put ingots which were not good before my messenger (Sit-Sin) and said: “If you want to take them, take them; if you do not want to take them, go away!” What do you take me for, that you treat somebody like me with such contempt?

I have sent as messengers gentlemen like ourselves to collect the bag with my money (deposited with you) but you have treated me with contempt by sending them back to me empty-handed several times, and that through enemy territory. Is there anyone among the merchants who trade with Telmun who has treated me in this way? You alone treat my messenger with contempt! On account of that one (trifling) mina of silver which I owe(?) you, you feel free to speak in such a way, while I have given to the palace on your behalf 1,080 pounds of copper, and umi-abum has likewise given 1,080 pounds of copper, apart from what we both have had written on a sealed tablet to be kept in the temple of Samas.

How have you treated me for that copper? You have withheld my money bag from me in enemy territory; it is now up to you to restore (my money) to me in full. Take cognizance that (from now on) I will not accept here any copper from you that is not of fine quality. I shall (from now on) select and take the ingots individually in my own yard, and I shall exercise against you my right of rejection because you have treated me with contempt.

Marianne Mödlinger

Marianne Mödlinger is a prehistoric archaeologist. Her main research interests include Bronze Age studies, the manufacture and usage of Bronze Age arms and armour, archaeometallurgy of copper alloys, and experimental archaeology.